Allophanate carbamate azido-alkyne click compositions

ABSTRACT

An alternative polyurethane composition is provided comprising a reaction product of an azidated polyol and a poly(alkynyl carbamate) allophanate prepolymer, wherein the poly(alkynyl carbamate) allophanate prepolymer comprises a reaction product of a first alkynol and a poly(alkynyl carbamate) prepolymer, in the presence of a metallo-organic compound of the formula: M(acac)n, wherein, M=a metal, acac=an acetylacetonate residue, and n=2 or 3, wherein the poly(alkynyl carbamate) prepolymer comprises a reaction product of a polyisocyanate and a stoichiometric equivalent of a second alkynol, and wherein the polyisocyanate comprises isocyanate groups and uretdione groups. The inventive alternative polyurethane compositions may be used to provide solventborne or waterborne coatings, adhesives, sealants, films, elastomers, castings, foams, and composites.

FIELD OF THE INVENTION

The present invention relates to click chemistry compositions comprisingthe reaction product of a poly(alkynyl carbamate) and an azidatedpolyol. The poly(alkynyl carbamate) is the reaction product of analkynol and a polyisocyanate containing isocyanate groups and uretdionegroups. The compositions are suitable for use as coatings, adhesives,sealants, films, elastomers, castings, foams, and composites.

BACKGROUND OF THE INVENTION

“Click chemistry” is a term first used by Sharpless et al. (Angew. Chem.Int. Ed. 2001, 40, 2004-2021) to describe a family of syntheticreactions, which attempt to imitate nature by joining small moleculestogether with heteroatom links. Sharpless et al. stated a number ofcriteria that a reaction must meet to be considered a “click” typereaction. These criteria include the reaction (a) must be modular; (b)must have a wide scope; (c) must provide high yields; (d) must produceinoffensive by-products (which can be removed by non-chromatographicmethods); (e) must be stereospecific; and (f) must involve simplereaction conditions (insensitive to water and oxygen) and productisolation. Finally, the reaction should use readily available startingmaterials, reactants, and solvents which are easily removed.

One example of a click reaction which has attracted wide attention isthe copper catalyzed azide-alkyne cycloaddition (CuAAC). Thisazide-alkyne cycloaddition was first described by Huisgen in 1963 andwas carried out in the absence of a catalyst, requiring elevatedtemperatures and giving a mixture of products (namely the 1,4 and1,5-substituted triazoles). The Cu^(I)-catalyzed cycloaddition wasdiscovered independently by Meldal (Macromol. Rapid. Com. 2008, 29(12-13), 1016-1051) and Sharpless et al. The benefit seen with thesecopper-catalyzed reactions was that they could be performed at roomtemperature and resulted in the exclusive formation of 1,4-substitutedtriazole products. Another advantage of this cycloaddition is that theazide and alkyne moieties are generally unreactive towards a wide rangeof functional groups, which eliminates the need for extensive use ofprotecting groups. This advantage is a key to the reaction's popularityin a number of scientific fields such as the biomedical field andmaterial science.

Although the initial investigations of 1,3-dipolar cycloadditions viaclick chemistry focused on the functionalization and attachment of smallmolecules to biochemical molecules, U.S. Pat. No. 8,101,238 issued toFokin et al. describes adhesive polymers which are formed frompolyvalent alkynes and azides and can be assembled into cross-linkedpolymer networks by copper catalysis. The Fokin et al. patent describesthe formation of coatings on copper metal surfaces which act as acatalyst for the alkynes and azides to form linear polymers including upto 22 units of a diazide and dialkyne or cross-linked polymericnetworks. The compositions disclosed in Fokin et al. were proposed foruse in applications such as adhesives and coatings and for combinationwith cement and other materials.

Polymeric triazoles constructed by 1,3-dipolar cycloaddition are alsodescribed in U.S. Pat. No. 7,772,358 issued to Tang et al. The compoundsof Tang et al. are prepared by thermal conversion at about 100° C.without the addition of a catalyst, which resulted in the formation ofboth 1,4- and 1,5-disubstituted triazoles. These compositions aredescribed by Tang et al. as being “hyper-branched”, which is a result ofthe exclusive use of tri- or higher substituted alkynes and azidesduring preparation. The advantage of these compositions is that theirpreparation does not involve the use of additional solvents orcatalysts, which might have detrimental effects on the resultingproperties. This benefit, however, is somewhat negated by the need tocure the compositions at elevated temperatures.

Xin-Ming et al. (Biomacromolecules 2007, 8, 2653-2658) describe thesynthesis of linear poly(ethylene glycol)s using 1,3-dipolarcycloaddition for chain extension. Xin-Ming et al. disclose thatpoly(ethylene glycol)s having pendant alkyne moieties are reacted with2,2-bis(azidomethyl)propane-1,3,diol and copper sulfate/sodiumascorbate.

A significant disadvantage of the above-described reactions is therequired use of di- and polyazides, which have relatively high nitrogencontents. For example, Fokin et al. in U.S. Pat. No. 8,101,238 describecompounds having nitrogen contents of up to about 60% in the form ofazides. Such compounds are impracticable for industrial application dueto the compounds' explosiveness. The compounds of Tang et al. andXin-Ming et al. have nitrogen contents in the form of azides of about23% and 43%, respectively, which pose problems when the azide compoundsare handled as such.

Ossipov et al. (Macromolecules 2006, 39, 1709-1718) describe thepreparation of poly(vinyl alcohol)-based hydrogels via 1,3-dipolarcycloaddition, in which a first poly(vinyl alcohol) is functionalizedwith azide functionalities and a second poly(vinyl alcohol) isfunctionalized with alkyne functionalities, and subsequently the twopoly(vinyl alcohol)s are reacted with each other by cyclization of thealkyne and azide groups. Ossipov et al. also disclose that azideterminated poly(ethylene glycol)s may be used as a replacement for theazide-modified poly(vinylalcohol).

Carter et al. in U.S. Pat. No. 9,790,398 disclose the synthesis of botha diazide monomer and a dialkyne monomer from 4,4′-diphenylmethanediisocyanate (MDI). The inventors also created a diazide monomer byreaction of sodium azide with diglycidyl ether of poly(propylene oxide).Carter et al. disclose the synthesis of only one polymer produced byCuAAC catalyzed reaction of azide-functional poly(propylene glycol)diglycidyl ether with the dialkyne of MDI.

U.S. Pat. Pub. No. 2016/0311973 in the name of Yang et al. is directedto waterborne dispersion coatings that cure by a 1,3-dipolarcycloaddition. Yang et al. disclose hexamethylene diisocyanate(HDI)-based polyurethane/urea dispersions possessing pendent propargylgroups, HDI-based polyurethane/urea dispersions possessing pendent azidegroups, and also alkyd and acrylic type waterborne polymers possessingeither alkyne or azide pendent groups.

Both the Carter et al. and Yang et al. references start from smallmolecules and polymerize these materials to give the final alternativepolyurethane products.

Despite the above-described advancements in technology, the 1,3-dipolarcycloaddition of multivalent azides and alkynes has not been describedin combination with prepolymer precursors to which the azide and alkynegroups have been attached. Such prepolymers would have the advantagethat the azide content of a prepolymer relative to its total weightcould be low enough to minimize the risk of explosions, while the numberof azides in the prepolymer molecules can be higher than two allowingthe formation of cross-linked systems.

To reduce or eliminate problem(s), therefore, a need continues to existin the art for ways of producing alternative polyurethane compositionswhich rely on simple modification of existing prepolymers.

SUMMARY OF THE INVENTION

Accordingly, the present invention reduces or eliminates problemsinherent in the art by providing novel chemical intermediates andmethods of preparation, and polyurethane-based coatings, adhesives,sealants, films, elastomers, castings, foams, and composites madetherefrom, that cure without the presence of free isocyanates in thefinal curing step. Curing of the inventive coatings, adhesives,sealants, films, elastomers, castings, foams, and composites,collectively the inventive alternative polyurethane compositions,involves reaction of an alkyne-functional resin with an azide-functionalresin (i.e. Huisgen azido-alkyne cycloaddition) and may be carried outat elevated temperatures in the absence of a catalyst. The inventivealternative polyurethane compositions are made from a polyisocyanatecomprising isocyanate groups and uretdione groups and the inventivecompositions may be used in the production of coatings, adhesives,sealants, films, elastomers, castings, foams, and composites which maybe solvent-borne or waterborne.

These and other advantages and benefits of the present invention will beapparent from the Detailed Description of the Invention herein below.

DETAILED DESCRIPTION OF THE INVENTION

The present invention will now be described for purposes of illustrationand not limitation. Except in the operating examples, or where otherwiseindicated, all numbers expressing quantities, percentages, and so forthin the specification are to be understood as being modified in allinstances by the term “about.”

Any numerical range recited in this specification is intended to includeall sub-ranges of the same numerical precision subsumed within therecited range. For example, a range of “1.0 to 10.0” is intended toinclude all sub-ranges between (and including) the recited minimum valueof 1.0 and the recited maximum value of 10.0, that is, having a minimumvalue equal to or greater than 1.0 and a maximum value equal to or lessthan 10.0, such as, for example, 2.4 to 7.6. Any maximum numericallimitation recited in this specification is intended to include alllower numerical limitations subsumed therein and any minimum numericallimitation recited in this specification is intended to include allhigher numerical limitations subsumed therein. Accordingly, Applicantreserves the right to amend this specification, including the claims, toexpressly recite any sub-range subsumed within the ranges expresslyrecited herein. All such ranges are intended to be inherently describedin this specification such that amending to expressly recite any suchsub-ranges would comply with the requirements of 35 U.S.C. § 112(a), and35 U.S.C. § 132(a). The various embodiments disclosed and described inthis specification can comprise, consist of, or consist essentially ofthe features and characteristics as variously described herein.

Any patent, publication, or other disclosure material identified hereinis incorporated by reference into this specification in its entiretyunless otherwise indicated, but only to the extent that the incorporatedmaterial does not conflict with existing definitions, statements, orother disclosure material expressly set forth in this specification. Assuch, and to the extent necessary, the express disclosure as set forthin this specification supersedes any conflicting material incorporatedby reference herein. Any material, or portion thereof, that is said tobe incorporated by reference into this specification, but whichconflicts with existing definitions, statements, or other disclosurematerial set forth herein, is only incorporated to the extent that noconflict arises between that incorporated material and the existingdisclosure material. Applicant reserves the right to amend thisspecification to expressly recite any subject matter, or portionthereof, incorporated by reference herein.

Reference throughout this specification to “various non-limitingembodiments,” “certain embodiments,” or the like, means that aparticular feature or characteristic may be included in an embodiment.Thus, use of the phrase “in various non-limiting embodiments,” “incertain embodiments,” or the like, in this specification does notnecessarily refer to a common embodiment, and may refer to differentembodiments. Further, the particular features or characteristics may becombined in any suitable manner in one or more embodiments. Thus, theparticular features or characteristics illustrated or described inconnection with various or certain embodiments may be combined, in wholeor in part, with the features or characteristics of one or more otherembodiments without limitation. Such modifications and variations areintended to be included within the scope of the present specification.

The grammatical articles “a”, “an”, and “the”, as used herein, areintended to include “at least one” or “one or more”, unless otherwiseindicated, even if “at least one” or “one or more” is expressly used incertain instances. Thus, these articles are used in this specificationto refer to one or more than one (i.e., to “at least one”) of thegrammatical objects of the article. By way of example, and withoutlimitation, “a component” means one or more components, and thus,possibly, more than one component is contemplated and may be employed orused in an implementation of the described embodiments. Further, the useof a singular noun includes the plural, and the use of a plural nounincludes the singular, unless the context of the usage requiresotherwise.

In a first aspect, the present invention is directed to a poly(alkynylcarbamate) allophanate prepolymer comprising a reaction product of afirst alkynol and a poly(alkynyl carbamate) prepolymer, in the presenceof a metallo-organic compound of the formula: M(acac)_(n), wherein, M=ametal, acac=an acetylacetonate residue, and n=2 or 3, wherein thepoly(alkynyl carbamate) prepolymer comprises a reaction product of apolyisocyanate and a stoichiometric equivalent of a second alkynol, andwherein the polyisocyanate comprises isocyanate groups and uretdionegroups.

In a second aspect, the present invention is directed to an alternativepolyurethane composition comprising a reaction product of an azidatedpolyol and the poly(alkynyl carbamate) allophanate prepolymer accordingto the previous paragraph.

In a third aspect, the present invention is directed to one of acoating, an adhesive, a sealant, a film, an elastomer, a casting, afoam, and a composite comprising the alternative polyurethanecomposition according to the previous paragraph.

In a fourth aspect, the present invention is directed to a substratehaving applied thereto the one of a coating, an adhesive, a sealant, afilm, an elastomer, a casting, a foam, and a composite according to theprevious paragraph.

In a fifth aspect, the present invention is directed to a process ofproducing an alternative polyurethane composition, the processcomprising reacting an azidated polyol and a poly(alkynyl carbamate)allophanate prepolymer, optionally in the presence of a catalyst,wherein the poly(alkynyl carbamate) allophanate prepolymer comprises areaction product of poly(alkynyl carbamate) prepolymer and a firstalkynol in the presence of a metallo-organic compound of the formula:M(acac)_(n), wherein M=a metal, acac=an acetylacetonate residue, and n=2or 3, wherein the poly(alkynyl carbamate) prepolymer comprises areaction product of a polyisocyanate and a stoichiometric equivalent ofa second alkynol, and wherein the polyisocyanate comprises isocyanategroups and uretdione groups.

In a sixth aspect, the present invention is directed to one of acoating, an adhesive, a sealant, a film, an elastomer, a casting, afoam, and a composite comprising the alternative polyurethanecomposition made according to the process of the previous paragraph.

In a seventh aspect, the present invention is directed to a substratehaving applied thereto the one of a coating, an adhesive, a sealant, afilm, an elastomer, a casting, a foam, and a composite according to theprevious paragraph.

Suitable poly(alkynyl carbamate) allophanate resins may be prepared intwo steps by: 1) reaction of both isocyanate groups of a polyisocyanateresin such as, for example, DESMODUR N3400, DESMODUR XP 2730 (aliphaticHDI uretdiones), CRELAN EF 403, CRELAN VP LS 2256 (aliphatic IPDIuretdiones), all available from Covestro, and THANECURE T9SF (aromaticTDI uretdione), available from TSE Industries, with a stoichiometricequivalent of an alkynol in the presence of a catalytic amount ofdibutyltin dilaurate to produce a poly(alkynyl carbamate) resin; and 2)reaction of the uretdione groups with a stoichiometric equivalent of thesame or a different alkynol in the presence of a catalytic amount ofmetal acetylacetonate to produce a poly(alkynyl carbamate) allophanateprepolymer. Suitable azide-functional resins may be prepared byconversion of polyol resins (e.g., DESMOPHEN 650A, PPG 1000, PPG 2000,SETALUX D A 870 BA) to azidated resins by first reacting the polyolresin with methane sulfonyl chloride in the presence of base followed bydisplacement of the methanesulfonate by an azide anion using NaN₃ underconditions favorable for S_(N)2 chemistry. Formulated mixtures of alkyneand azide resins may be cured at elevated temperatures (e.g. 100° C. to200° C.) with no catalyst to give coatings that have similar propertiesto their isocyanate-alcohol counterparts.

The metal acetylacetonate used to catalyze reaction of the uretdionegroups with an alkynol is an metallo-organic compound of the formula:

M(acac)_(n),

wherein,

M=a metal,

acac=an acetylacetonate residue, and

n=2 or 3.

In various embodiments, M is chosen from aluminum, calcium, chromium,cobalt, copper, iron, magnesium, manganese, nickel, titanium, vanadium,zinc, and zirconium. In a selected embodiment, the metallo-organiccompound is zinc acetylacetonate.

As used herein, the term “polymer” encompasses prepolymers, oligomers,and both homopolymers and copolymers; the prefix “poly” in this contextrefers to two or more. As used herein, the term “molecular weight”, whenused in reference to a polymer, refers to the number average molecularweight, unless otherwise specified.

As used herein, the term “polyol” refers to compounds comprising atleast two free hydroxyl groups. Polyols include polymers comprisingpendant and terminal hydroxyl groups.

As used herein, the term “coating composition” refers to a mixture ofchemical components that will cure and form a coating when applied to asubstrate.

The terms “adhesive” or “adhesive composition” refer to any substancethat can adhere or bond two items together. Implicit in the definitionof an “adhesive composition” or “adhesive formulation” is the conceptthat the composition or formulation is a combination or mixture of morethan one species, component or compound, which can include adhesivemonomers, oligomers, and polymers along with other materials.

A “sealant” or “sealant composition” refers to a composition which maybe applied to one or more surfaces to form a protective barrier, forexample to prevent ingress or egress of solid, liquid or gaseousmaterial or alternatively to allow selective permeability through thebarrier to gas and liquid. In particular, it may provide a seal betweensurfaces.

A “film composition” refers to a mixture of chemical components thatwill cure and form a thin flexible strip of material, i.e., a “film”.

An “elastomer” refers to a polymeric composition that has highelongation and flexibility or elasticity. Elastomers may be made fromnatural rubber, polyurethanes, polybutadiene, neoprene, and silicone.

A “casting” or “casting composition” refers to a mixture of liquidchemical components which is usually poured into a mold containing ahollow cavity of the desired shape, and then allowed to solidify.

A “foam” is produced by mixing a polyol and an isocyanate along with anamine or organometallic catalyst and a combination of water and ahydrofluorocarbon blowing agent.

A “composite” or “composite composition” refers to a material made fromone or more polymers, containing at least one other type of material(e.g., a fiber) which retains its identity while contributing desirableproperties to the composite. A composite has different properties fromthose of the individual polymers/materials which make it up.

The terms “cured,” “cured composition” or “cured compound” refer tocomponents and mixtures obtained from reactive curable originalcompound(s) or mixture(s) thereof which have undergone chemical and/orphysical changes such that the original compound(s) or mixture(s)is(are) transformed into a solid, substantially non-flowing material. Atypical curing process may involve crosslinking.

The term “curable” means that an original compound(s) or compositionmaterial(s) can be transformed into a solid, substantially non-flowingmaterial by means of chemical reaction, crosslinking, radiationcrosslinking, or the like. Thus, compositions of the invention arecurable, but unless otherwise specified, the original compound(s) orcomposition material(s) is(are) not cured.

As used herein, the term “solventborne” refers to a composition, whichcontains organic solvents rather than water as its primary liquidcomponent.

As used herein, the term “waterborne” refers to a composition whichcontains water as its primary liquid component.

The components useful in the present invention comprise apolyisocyanate. As used herein, the term “polyisocyanate” refers tocompounds comprising at least two unreacted isocyanate groups, such asthree or more unreacted isocyanate groups. The polyisocyanate maycomprise diisocyanates such as linear aliphatic polyisocyanates,aromatic polyisocyanates, cycloaliphatic polyisocyanates and aralkylpolyisocyanates.

Suitable polyisocyanates for use in embodiments of the invention includeorganic diisocyanates represented by the formula

R(NCO)₂

wherein R represents an organic group obtained by removing theisocyanate groups from an organic diisocyanate having(cyclo)aliphatically bound isocyanate groups and a molecular weight of112 to 1000, preferably 140 to 400. Preferred diisocyanates for theinvention are those represented by the formula wherein R represents adivalent aliphatic hydrocarbon group having from 4 to 18 carbon atoms, adivalent cycloaliphatic hydrocarbon group having from 5 to 15 carbonatoms, or a divalent araliphatic hydrocarbon group having from 7 to 15carbon atoms.

Examples of the organic diisocyanates which are particularly suitablefor the present invention include 1,4-tetramethylene diisocyanate,1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylenediisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3- and1,4-diisocyanate, 1-isocyanato-2-isocyanato-methyl cyclopentane,1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane (isophoronediisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)methane, 1,3- and1,4-bis(isocyanatomethyl)-cyclohexane,bis-(4-isocyanato-3-methyl-cyclohexyl)-methane,α,α,α′,α′-tetramethyl-1,3- and 1,4-xylene diisocyanate,1-isocyanato-1-methyl-4(3)-isocyanato-methyl cyclohexane, and 2,4- and2,6-hexahydrotoluene diisocyanate, toluene diisocyanate (TDI),diphenylmethane diisocyanate (MDI), pentane diisocyanate(PDI)—bio-based), and, isomers of any of these; or combinations of anyof these. Mixtures of diisocyanates may also be used. Preferreddiisocyanates include 1,6-hexamethylene diisocyanate, isophoronediisocyanate, and bis(4-isocyanatocyclohexyl)-methane because they arereadily available and yield relatively low viscosity oligomers.

The polyols useful in the present invention may be either low molecularweight (62-399 Da, as determined by gel permeation chromatography) orhigh molecular weight (400 to 10,000 Da, as determined by gel permeationchromatography) materials and in various embodiments will have averagehydroxyl values as determined by ASTM E222-17, Method B, of between 1000and 10, and preferably between 500 and 50.

The polyols in the present invention include low molecular weight diols,triols and higher alcohols and polymeric polyols such as polyesterpolyols, polyether polyols, polycarbonate polyols, polyurethane polyolsand hydroxy-containing (meth)acrylic polymers.

The low molecular weight diols, triols, and higher alcohols useful inthe present invention are known to those skilled in the art. In manyembodiments, they are monomeric and have hydroxyl values of 200 andabove, usually within the range of 1500 to 200. Such materials includealiphatic polyols, particularly alkylene polyols containing from 2 to 18carbon atoms. Examples include ethylene glycol, 1,4-butanediol,1,6-hexanediol, and cycloaliphatic polyols such as cyclohexanedimethanol. Examples of triols and higher alcohols include trimethylolpropane and pentaerythritol. Also useful are polyols containing etherlinkages such as diethylene glycol and triethylene glycol.

In various embodiments, the suitable polyols are polymeric polyolshaving hydroxyl values less than 200, such as 10 to 180. Examples ofpolymeric polyols include polyalkylene ether polyols, polyester polyolsincluding hydroxyl-containing polycaprolactones, hydroxy-containing(meth)acrylic polymers, polycarbonate polyols and polyurethane polymers.

Examples of polyether polyols include poly(oxytetramethylene) glycols,poly(oxyethylene) glycols, and the reaction product of ethylene glycolwith a mixture of propylene oxide and ethylene oxide.

Also useful are polyether polyols formed from the oxyalkylation ofvarious polyols, for example, glycols such as ethylene glycol,1,4-butane glycol, 1,6-hexanediol, and the like, or higher polyols, suchas trimethylol propane, pentaerythritol and the like. One commonlyutilized oxyalkylation method is reaction of a polyol with an alkyleneoxide, for example, ethylene oxide in the presence of an acidic or basiccatalyst.

Polyester polyols can also be used as a polymeric polyol component inthe certain embodiments of the invention. The polyester polyols can beprepared by the polyesterification of organic polycarboxylic acids oranhydrides thereof with organic polyols. Preferably, the polycarboxylicacids and polyols are aliphatic or aromatic dibasic acids and diols.

The diols which may be employed in making the polyester include alkyleneglycols, such as ethylene glycol and butylene glycol, neopentyl glycoland other glycols such as cyclohexane dimethanol, caprolactone diol (forexample, the reaction product of caprolactone and ethylene glycol),polyether glycols, for example, poly(oxytetramethylene) glycol and thelike. However, other diols of various types and, as indicated, polyolsof higher functionality may also be utilized in various embodiments ofthe invention. Such higher polyols can include, for example, trimethylolpropane, trimethylol ethane, pentaerythritol, and the like, as well ashigher molecular weight polyols such as those produced by oxyalkylatinglow molecular weight polyols. An example of such high molecular weightpolyol is the reaction product of 20 moles of ethylene oxide per mole oftrimethylol propane.

The acid component of the polyester consists primarily of monomericcarboxylic acids or anhydrides having 2 to 18 carbon atoms per molecule.Among the acids which are useful are phthalic acid, isophthalic acid,terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid,adipic acid, azelaic acid, sebacic acid, maleic acid, glutaric acid,chlorendic acid, tetrachlorophthalic acid and other dicarboxylic acidsof varying types. Also, there may be employed higher polycarboxylicacids such as trimellitic acid and tricarballylic acid (where acids arereferred to above, it is understood that the anhydrides of those acidswhich form anhydrides can be used in place of the acid). Also, loweralkyl esters of acids such as dimethyl glutamate can be used.

In addition to polyester polyols formed from polybasic acids andpolyols, polycaprolactone-type polyesters can also be employed. Theseproducts are formed from the reaction of a cyclic lactone such asε-caprolactone with a polyol with primary hydroxyls such as thosementioned above. Such products are described in U.S. Pat. No. 3,169,949.

In addition to the polyether and polyester polyols, hydroxy-containing(meth)acrylic polymers or (meth)acrylic polyols can be used as thepolyol component.

Among the (meth)acrylic polymers are polymers of 2 to 20 percent byweight primary hydroxy-containing vinyl monomers such as hydroxyalkylacrylate and methacrylate having 2 to 6 carbon atoms in the alkyl groupand 80 to 98 percent by weight of other ethylenically unsaturatedcopolymerizable materials such as alkyl(meth)acrylates; the percentagesby weight being based on the total weight of the monomeric charge.

Examples of suitable hydroxyalkyl (meth)acrylates are hydroxy ethyl andhydroxy butyl(meth)acrylate. Examples of suitable alkyl acrylates and(meth)acrylates are lauryl methacrylate, 2-ethylhexyl methacrylate andn-butyl acrylate.

In addition to the acrylates and methacrylates, other copolymerizablemonomers which can be copolymerized with the hydroxyalkyl(meth)acrylates include ethylenically unsaturated materials such asmonoolefinic and diolefinic hydrocarbons, halogenated monoolefinic anddiolefinic hydrocarbons, unsaturated esters of organic and inorganicacids, amides and esters of unsaturated acids, nitriles and unsaturatedacids and the like. Examples of such monomers include styrene,1,3-butadiene, acrylamide, acrylonitrile, α-methyl styrene, α-methylchlorostyrene, vinyl butyrate, vinyl acetate, alkyl chloride, divinylbenzene, diallyl itaconate, triallyl cyanurate and mixtures thereof. Invarious embodiments, these other ethylenically unsaturated materials areused in admixture with the above-mentioned acrylates and methacrylates.

In certain embodiments of the invention, the polyol may be apolyurethane polyol. These polyols can be prepared by reacting any ofthe above-mentioned polyols with a minor amount of polyisocyanate(OH/NCO equivalent ratio greater than 1:1) so that free primary hydroxylgroups are present in the product. In addition to the high molecularweight polyols mentioned above, mixtures of both high molecular weightand low molecular weight polyols such as those mentioned above may beused.

Suitable hydroxy-functional polycarbonate polyols may be those preparedby reacting monomeric diols (such as 1,4-butanediol, 1,6-hexanediol,di-, tri- or tetraethylene glycol, di-, tri- or tetrapropylene glycol,3-methyl-1,5-pentanediol, 4,4′-dimethylolcyclohexane and mixturesthereof) with diaryl carbonates (such as diphenyl carbonate, dialkylcarbonates (such as dimethyl carbonate and diethyl carbonate), alkylenecarbonates (such as ethylene carbonate or propylene carbonate), orphosgene. Optionally, a minor amount of higher functional, monomericpolyols, such as trimethylolpropane, glycerol or pentaerythritol, may beused.

In various embodiments, the azidated polyols are the reaction productsof a polyol and methane sulfonyl chloride (or toluenesulfonyl (tosyl),p-bromophenylsulfonyl (brosyl), benzyl) in presence of base, followed bydisplacement of the methanesulfonate by an azide anion using NaN₃.Another method to produce azidated polyols is the reaction of apolyoxirane compound, for example, a (meth)acrylic polymer containingglycidyl methacrylate comonomer units, with an azide ion using, forexample, NaN₃. Any polyol, including but not limited to, those disclosedherein may be azidated and useful in the invention.

The azidated polyol useful in the present application may have anitrogen content derivable from azide relative to the total weight ofthe molecule in various embodiment of 20 wt.-% or less, in certainembodiments of 18 wt.-% or less, or of 16 wt.-% or less and in selectedembodiments of 15 wt.-% or less. Having such a low azide content helpsto ensure that the polyols are sufficiently stable against explosivedecomposition, such that extensive handling precautions can be avoided.On the other hand, it is preferred that the nitrogen content derivablefrom azide relative to the total weight of the molecule in the azidatedpolyol in various embodiments is 1 wt.-% or more, in some embodiments, 2wt.-% or more, in certain embodiments, 5 wt.-% or more and in selectedembodiments, 8 wt.-% or more. Such an azide content ensures that thepolyols have a sufficiently low viscosity during handling, but alsopermits the azidated polyol to contain multiple azide groups.

The alkyne compound useful in the present invention may be prepared bythe reaction of an epoxy compound and an alkyne having functional groupsreactive towards epoxies. The resulting product may subsequently bereacted with an alkyne group-containing alkylation agent to obtain analkyne compound having two or more alkyne groups. In variousembodiments, the functional group reactive toward epoxies is an amine ora thiol group, but hydroxyl or carboxyl groups may also be employed asfunctional groups.

In various embodiments, the alkyne-containing alkylation agent is apropargyl halogenide, in certain embodiments, a propargyl chloride orbromide, as such compounds are readily available and relativelyinexpensive.

In selected embodiments, the alkyne is obtainable by the reaction of apolyisocyanate or isocyanate-terminated polyurethane prepolymer and analkyne having a functional group reactive towards isocyanates. Thefunctional group reactive towards isocyanates may be an amine, hydroxylor thiol group. The alkyne may be straight chain or branched and containcyclic moieties. In various embodiments, the alkyne contains from 3 to10 carbon atoms; in other embodiments from 3 to 8 carbon atoms. Apreferred alkyne for the reaction with polyisocyanates or polyisocyanateprepolymer is propargyl alcohol.

In certain embodiments, the optional catalyst in the present applicationmay be a Cu^(I)-based catalyst. The Cu^(I)-based catalyst may, forexample, be a copper-containing surface which contains sufficient Cu^(I)in the surface layer to provide the required catalytic action. Ifapplication of the inventive composition to non copper-containingsurfaces is intended, it is necessary that the Cu^(I)-based catalystcome from a copper source which is not attached to the surface of amaterial to which the alternative polyurethane composition is to beapplied.

Suitable copper catalysts of this type can be based on commerciallyavailable Cu^(I) salts such as CuBr or CuI. It has been noted thatCu^(I) precursors do not provide catalysts with high reactivities in theformation of 1,4-disubstituted triazoles when azide compounds having twoor more azide groups attached thereto and alkyne compounds having two ormore alkyne groups attached to a molecule are reacted; however, Cu_(II)precursors which are converted to Cu^(I) by the action of a reducingagent, provide enhanced activity. Suitable Cu^(II) precursors include,but are not limited to, copper(II) sulfate, copper(II) acetatemonohydrate, and copper(II) 2-ethylhexanoate. Suitable reducing agentsinclude, for example, triphenyl phosphine, sodium ascorbate, tin(II)2-ethylhexanoate and hydroquinone.

The alternative polyurethane compositions of the present invention areobtainable by reacting an azidated polyol having two or more azidegroups attached thereto and an alkyne compound having two or more alkynegroups attached thereto in a 1,4-dipolar cycloaddition of the azide andalkyne groups. This can, for example, be achieved by heating thecomponents to temperatures sufficient to affect the cycloaddition suchas in various embodiments, at least 100° C., in certain embodiments, atleast 140° C. and in selected embodiments, at least 200° C.

In various embodiments, the alternative polyurethane compositions of thepresent invention may be used to provide coatings, adhesives, sealants,films, elastomers, castings, foams, and composites.

The alternative polyurethane compositions of the present invention mayfurther include any of a variety of additives such as defoamers,devolatilizers, surfactants, thickeners, flow control additives,colorants (including pigments and dyes) or surface additives.

The alternative polyurethane compositions of the invention may becontacted with a substrate by any methods known to those skilled in theart, including but not limited to, spraying, dipping, flow coating,rolling, brushing, pouring, and the like. In some embodiments, theinventive compositions may be applied in the form of paints or lacquersonto any compatible substrate, such as, for example, metals, plastics,ceramics, glass, and natural materials. In certain embodiments, theinventive composition is applied as a single layer. In otherembodiments, the composition of the present invention may be applied asmultiple layers as needed.

EXAMPLES

The non-limiting and non-exhaustive examples that follow are intended tofurther describe various non-limiting and non-exhaustive embodimentswithout restricting the scope of the embodiments described in thisspecification. All quantities given in “percents” are understood to beby weight, unless otherwise indicated. For the purpose of mass to moleconversions, reagents with purity of 99% or higher are considered to be100% pure.

Although described herein in the context of a coating, those skilled inthe art will recognize that the principles of the present invention areequally applicable to adhesives, sealants, films, elastomers, castings,foams, and composites.

The following materials were used in preparation of the Examples:

POLYISOCYANATE A a low viscosity, solvent-free aliphatic polyisocyanate(HDI uretdione) resin, 195.44 g/equiv. isocyanate, 528.22 g/equiv.uretdione, commercially available from Covestro LLC (Pittsburgh, PA) asDESMODUR N3400 (21.5% NCO); POLYOL A an acrylic polyol, received as an80% solids solution in n-BA. commercially available from Allnex asSETALUX DA 870 BA, possessing hydroxyl equivalent weight of 461.02 g/eq(at 100% solids); AZIDATED POLYOL A a proprietary prepolymer based onPOLYOL A, having azide equivalent weight of 522.71 g/eq (at 92.98%solids); the solid % was determined by drying an aliquot in an oven andrecording the fraction weight remaining; POLY(ALKYNYL a proprietaryprepolymer based on CARBAMATE) A POLYISOCYANATE A, having alkyneequivalent PREPOLYMER weight of 251.50 g/eq.; POLY(ALKYNYL a proprietaryallophanate prepolymer based on CARBAMATE) POLY(ALKYNYL CARBAMATE) APREPOLYMER ALLOPHANATE A made in the presence of METALLO-ORGANICPREPOLYMER COMPOUND A, having alkyne equivalent weight of 198.72 g/eq.;4 Å Molecular Sieves Fisher Scientific, Type 4A, Grade 514, 8-12 Meshbeads, 4 Å pore size, activated using a microwave oven prior to use;ALKYNOL A propargyl alcohol (99%), commercially available from FisherScientific; reagent was dried over 4 Å molecular sieves prior to use;TEA triethylamine (≥99.5%), commercially available from Sigma-Aldrich;reagent was dried over 4 Å molecular sieves prior to use; MeCNacetonitrile (OPTIMA), commercially available from Fisher Scientific;solvent was distilled and dried over 4 Å molecular sieves prior to use;Mesyl-Cl methanesulfonyl chloride (≥99.7%), commercially available fromSigma-Aldrich; DCM dichloromethane (Certified ACS), commerciallyavailable from Fisher Scientific; DMF N,N-dimethylformamide (CertifiedACS), commercially available from Fisher Scientific; NaN₃ sodium azide(REAGENTPLUS, ≥99.5%), commercially available from Sigma-Aldrich; n-BAn-butyl acetate, ACS reagent, ≥99.5%, commercially available fromSigma-Aldrich, solvent was dried over 4 Å molecular sieves prior to use;MEK methyl ethyl ketone, Certified ACS, commercially available fromSigma-Aldrich; Ethyl acetate Certified ACS, commercially available fromFisher Scientific; CATALYST A dibutyltin dilaurate (DBTDL, 98%),commercially available from Strem Chemicals; METALLO-ORGANIC zinc(II)acetylacetonate (Zn(acac)₂, ≥95.0%), COMPOUND A commercially availablefrom Sigma-Aldrich; Brine saturated aqueous solution of NaCl, preparedby dissolving 450 g NaCl (certified ACS, Fisher Scientific) into 1.2 Lof DI water at room temperature; and MgSO₄ magnesium sulfate, anhydrous,commercially available from Fisher Scientific.

Synthesis of POLY(ALKYNYL CARBAMATE) A PREPOLYMER

All glassware was cleaned and dried in an oven overnight. The followingprocedure was performed in a N₂-protected dry box equipped with acryostated heptane bath. POLYISOCYANATE A (100.0 g, 0.512 molisocyanate) and CATALYST A (1.0 g) were charged to a 500 mL, three-neckround bottom flask equipped with a mechanical stirrer, a thermocouple,and an addition funnel. The contents of the flask were stirred andallowed to equilibrate at 0° C. for ten minutes. After equilibration,ALKYNOL A (28.684 g, 0.512 mol) was charged to the addition funnel andadded into the stirred solution at initially 1 drop/sec. The additionspeed was adjusted so that the temperature of the reaction would notexceed 30° C. After the addition, the mixture was allowed to reactovernight, and the product of the reaction was characterized by FTIR and¹³C-NMR, and ¹H-NMR.

Synthesis of POLY(ALKYNYL CARBAMATE) ALLOPHANATE A PREPOLYMER UretdioneRing-Opening Reaction of POLY(ALKYNYL CARBAMATE) A PREPOLYMER

All glassware was cleaned and dried in an oven overnight. POLY(ALKYNYLCARBAMATE) A PREPOLYMER (96.51 g, 0.142 mol uretdione), ALKYNOL A (11.0g, 0.196 mol), and METALLO-ORGANIC COMPOUND A (1.0 g) were charged to a500 mL, one-neck, round bottom flask equipped with a stirrer and acondenser sealed with a rubber septum with a needle. The system wasstirred and heated to reflux at 105° C., and allowed to react for fourhours. The excess ALKYNOL A was vacuum stripped, and the product of thereaction was characterized by ¹³C-NMR and ¹H-NMR.

Synthesis of AZIDATED POLYOL A

All glassware was cleaned and dried in an oven overnight. The followingprocedure was performed in a N₂-protected dry box equipped with acryostated heptane bath. POLYOL A (150.1 g, 0.260 mol), TEA (55.0 mL,0.395 mol), and MeCN (300 mL) were charged to a one-liter, two-neckround bottom flask equipped with a mechanical stirrer and an additionfunnel. The mixture was stirred and allowed to equilibrate at 0° C. for10 minutes. After equilibration, a solution of mesyl-Cl (24.0 mL, 0.310mol) in MeCN (50 mL) was charged to the addition funnel and added intothe stirring solution at 1 drop/sec. After the addition, the mixture wasallowed to react overnight.

The reaction flask was transferred out of the dry box, and the mixturewas filtered to remove the TEA salts. MeCN and excess TEA were vacuumstripped, and the mesylated resin was re-dissolved into ethyl acetate(500 mL). The solution was washed with 20/80 (v/v) brine/DI watermixture (3×300 mL) and then brine (300 mL) and dried with MgSO₄overnight. Ethyl acetate was removed by vacuum stripping to afford themesylated POLYOL A as an intermediate. An aliquot was taken to performFTIR, ¹³C and ¹H-NMR characterization.

The mesylated resin was re-dissolved in MeCN (300 mL) and DMF (30 mL),in a one liter, one-neck round bottom flask. NaN₃ (20.0 g, 0.308 mol)and a stir bar were added to the mixture, and the flask was equippedwith a condenser sealed with a rubber septum with a needle. The mixturewas stirred at 95° C. for 16 hours, allowed to cool to room temperature,and filtered to remove the Na mesylate salts. MeCN was vacuum stripped,and the azidated resin was re-dissolved into ethyl acetate (500 mL). Thesolution was washed with 20/80 (v/v), brine/water mixture (3×300 mL) andthen brine (3×300 mL) and dried with MgSO₄ overnight. The final product,AZIDATED POLYOL A, was isolated by removal of ethyl acetate by vacuumstripping and thereafter characterized by FTIR, ¹³C-NMR, and ¹H-NMR. Analiquot of the product was placed on an aluminum pan and dried in theoven at 100° C. for one hour.

Fourier transform infrared spectroscopy (FTIR) studies were conductedusing a NICOLET 8700 spectrometer with a KBr beam splitter and a DTGSdetector. Samples were sandwiched between two NaCl salt plates (polishedwith DCM) of approximate thickness of 5 mm.

Proton nuclear magnetic resonance (¹H NMR) spectra and carbon nuclearmagnetic resonance (¹³C NMR) spectra were obtained using a 600.13 MHzVarian Mercury^(Plus) NMR (VNMR 6.1C) spectrometer. For ¹H NMR, typicalacquisition parameters were 8 s recycle delay, 7.8 μs pulsecorresponding to a 45° flip angle, and an acquisition time of 1.998 s.The number of scans acquired for each sample was 64. All ¹H chemicalshifts were referenced to tetramethylsilane (TMS) (0 ppm). Samplesolutions were prepared at a concentration of approximately 5-10% indeuterated chloroform (CDCl₃) (99.8+ atom % D, 0.03 v/v % TMS) (AcrosOrganics, further dried using activated molecular sieves prior to use),and the resulting solution was charged to a 5 mm NMR tube.

For ¹³C NMR, typical acquisition parameters were 1 second recycle delay,11 ms pulse corresponding to a 45° flip angle, and an acquisition timeof 0.908 s. The number of scans acquired for each sample was 1024. All¹³C chemical shifts were referenced to residual chloroform (77.16 ppm).Sample solutions were prepared at a concentration of approximately 30%in CDCl₃, and the resulting solution was charged to a 5 mm NMR tube.

Differential scanning calorimetry (DSC) was performed using a TAInstruments Q200. For this purpose, coatings were prepared onpolyethylene (PE) film substrate. The coatings, which had littleadhesion to the PE film, were easily peeled off and punched to givecircular samples (d=0.25 in. (6.35 mm)) of the coating films. Stacks offive such samples (total ˜5 mg) per coating were placed in ahermetically sealed T_(zero) pan. A heat/cool/heat cycle was performedon each stack starting at −50° C. and ending at 200° C. at a rate of 10°C./min. The glass transition temperature (T_(g)) of the cured materialwas determined from the second heating cycle, and TA Universal Analysissoftware was used to determine the midpoint of the T_(g) inflection asthe reported value.

Coatings Preparation

FORMULATION A was prepared as follows. AZIDATED POLYOL A (3.039 g; 5.81mmol azide) and POLY(ALKYNYL CARBAMATE) A PREPOLYMER (1.462 g; 5.81 mmolalkyne) were added to a scintillation vial. The mixture was diluted withn-BA (0.225 g), placed in a FLAKTECH mixer and mixed at 1800 rpm for20-30 minutes until a homogeneous mixture was obtained. Meanwhile,smooth-finish steel panels (Type QD, Q-Lab Corporation) and polyethylene(PE) films were treated with acetone rinsing to remove surfacecontaminants. The mixture was drawn down onto the prepared panels and PEfilms using a 6 mil wet drawdown bar. The coatings were placed in a VWRShel lab HF2 oven and subjected to the following preprogrammed curingprofile: the solvent was allowed to flash at 30° C. for two hours, thenthe temperature was ramped up to 100° C. at 1° C./min. The coatings werecured at 100° C. for four hours and cooled to 30° C.

FORMULATION B was prepared as follows. AZIDATED POLYOL A (3.259 g; 6.23mmol azide) and POLY(ALKYNYL CARBAMATE) ALLOPHANATE A PREPOLYMER (1.239g; 6.23 mmol alkyne) were added to a scintillation vial. The mixture wasdiluted with n-BA (0.225 g), placed in a FLAKTECH mixer and mixed at1800 rpm for 20-30 minutes until a homogeneous mixture was obtained.Meanwhile, smooth-finish steel panels (Type QD, Q-Lab Corporation) andpolyethylene (PE) films were treated with acetone rinsing to removesurface contaminants. The mixture was drawn down onto the preparedpanels and PE films using a 6 mil wet drawdown bar. The coatings wereplaced in a VWR Shel lab HF2 oven and subjected to the followingpreprogrammed curing profile: the solvent was allowed to flash at 30° C.for two hours, then the temperature was ramped up to 100° C. at 1°C./min. The coatings were cured at 100° C. for four hours and cooled to30° C.

FORMULATION C was prepared as follows. POLYOL A (3.391 g; 5.88 mmol —OH)and POLYISOCYANATE A (1.150 g; 5.88 mmol —NCO) were added to ascintillation vial. The mixture was placed in a FLAKTECH mixer and mixedat 1800 rpm for 20-30 minutes until a homogeneous mixture was obtained.Meanwhile, smooth-finish steel panels (Type QD, Q-Lab Corporation) andpolyethylene (PE) films were treated with acetone rinsing to removesurface contaminants. The mixture was drawn down onto the preparedpanels and PE films using a 6 mil wet drawdown bar. The coatings wereplaced in a VWR Shel lab HF2 oven and subjected to the followingpreprogrammed curing profile: the solvent was allowed to flash at 30° C.for two hours, then the temperature was ramped up to 100° C. at 1°C./min. The coatings were cured at 100° C. for four hours and cooled to30° C.

Each coating formulation was applied onto three smooth-finish steelpanels (Type QD, Q-Lab Corporation). Each coating test was conducted intriplicate (one replicate per panel). Coating tests were performed 12hours after the complete curing profile.

MEK double rubs. Reaction conversion/crosslink density was qualitativelycompared via an MEK double rubs test up to 200 rubs using a 32 oz.(0.907 kg) hammer covered by four folds of cheesecloth according to ASTMD5402-15. Hardness was measured via a pencil hardness test in accordancewith ASTM D3363-05. Viscosities of the FORMULATIONS were measuredaccording to ASTM D7395-18 using a BROOKFIELD RST Rheometer at 25° C.,after 100 s⁻¹ shear rate for two minutes, and with a RST-50-1 spindle.

Performance properties of FORMULATION A and FORMULATION B coatings,compared to a control coating prepared using FORMULATION C, aresummarized below in Table I.

As can be seen from Table I, the performance of coatings made fromFORMULATION B is comparable to or better than coatings made fromFORMULATION A, as well as FORMULATION C, with respect to MEK doublerubs, glass transition temperature, and hardness (pencil hardness).

TABLE I FORMULATION A B C Pencil hardness 7H 7H 7H MEK double rubs 244,217, 210 400, 360, 210 281,295,300 T_(g)(DSC)/° C. 58.15 56.33 52.80

This specification has been written with reference to variousnon-limiting and non-exhaustive embodiments. However, it will berecognized by persons having ordinary skill in the art that varioussubstitutions, modifications, or combinations of any of the disclosedembodiments (or portions thereof) may be made within the scope of thisspecification. Thus, it is contemplated and understood that thisspecification supports additional embodiments not expressly set forthherein. Such embodiments may be obtained, for example, by combining,modifying, or reorganizing any of the disclosed steps, components,elements, features, aspects, characteristics, limitations, and the like,of the various non-limiting embodiments described in this specification.In this manner, Applicant reserves the right to amend the claims duringprosecution to add features as variously described in thisspecification, and such amendments comply with the requirements of 35U.S.C. § 112(a), and 35 U.S.C. § 132(a).

Various aspects of the subject matter described herein are set out inthe following numbered clauses:

Clause 1. A poly(alkynyl carbamate) allophanate prepolymer comprising areaction product of a first alkynol and a poly(alkynyl carbamate)prepolymer, in the presence of a metallo-organic compound of theformula: M(acac)_(n), wherein, M=a metal, acac=an acetylacetonateresidue, and n=2 or 3, wherein the poly(alkynyl carbamate) prepolymercomprises a reaction product of a polyisocyanate and a stoichiometricequivalent of a second alkynol, and wherein the polyisocyanate comprisesisocyanate groups and uretdione groups.

Clause 2. The poly(alkynyl carbamate) allophanate prepolymer accordingto Clause 1, wherein the first alkynol and the second alkynol eachindependently contain from 3 to 10 carbon atoms.

Clause 3. The poly(alkynyl carbamate) allophanate prepolymer accordingto one of Clauses 1 and 2, wherein the first alkynol and the secondalkynol are identical or different.

Clause 4. The poly(alkynyl carbamate) allophanate prepolymer accordingto any one of Clauses 1 to 3, wherein the first alkynol and the secondalkynol are selected from the group consisting of propargyl alcohol,2-hydroxyethylpropiolate, and isomers of any of these; or mixtures ofany of these.

Clause 5. The poly(alkynyl carbamate) allophanate prepolymer accordingto any one of Clauses 1 to 4, wherein M is selected from the groupconsisting of aluminum, calcium, chromium, cobalt, copper, iron,magnesium, manganese, nickel, titanium, vanadium, zinc, and zirconium.

Clause 6. The poly(alkynyl carbamate) allophanate prepolymer accordingto any one of Clauses 1 to 5, wherein the metallo-organic compoundcomprises zinc acetylacetonate.

Clause 7. The poly(alkynyl carbamate) allophanate prepolymer accordingto any one of Clauses 1 to 6, wherein the polyisocyanate is selectedfrom the group consisting of 1,4-tetramethylene diisocyanate,1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylenediisocyanate, 1,12-dodecamethylene diisocyanate,cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate,1-isocyanato-2-isocyanato-methyl cyclopentane,1-isocyanato-3-isocyanatomethyl-3,5,5-trimethyl cyclohexane (isophoronediisocyanate or IPDI), bis-(4-isocyanatocyclohexyl)methane,1,3-bis(isocyanatomethyl)-cyclohexane,1,4-bis(isocyanatomethyl)-cyclohexane,bis-(4-isocyanato-3-methyl-cyclohexyl)-methane,α,α,α′,α′-tetramethyl-1,3-xylene diisocyanate,α,α,α′,α′-tetramethy-1,4-xylene diisocyanate,1-isocyanato-1-methyl-4(3)-isocyanato-methyl cyclohexane,2,4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate,toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), pentanediisocyanate (PDI)—bio-based), and, isomers of any of these; or mixturesof any of these.

Clause 8. The poly(alkynyl carbamate) allophanate prepolymer accordingto any one of Clauses 1 to 7, wherein the uretdione groups are selectedfrom the group consisting of aliphatic 1,6-hexamethylene diisocyanate(HDI) uretdiones, aromatic toluene diisocyanate (TDI) uretdiones, andaliphatic isophorone diisocyanate (IPDI) uretdiones.

Clause 9. An alternative polyurethane composition comprising a reactionproduct of an azidated polyol and the poly(alkynyl carbamate)allophanate prepolymer according to any one of Clause 1 to 8, optionallyin the presence of a catalyst.

Clause 10. The alternative polyurethane composition according to Clause9, wherein the azidated polyol is a reaction product of a polyol and anazide.

Clause 11. The alternative polyurethane composition according to Clause10, wherein the polyol is selected from the group consisting ofpolyalkylene ether polyols, polyester polyols, hydroxyl containingpolycaprolactones, hydroxyl-containing (meth)acrylic polymers,polycarbonate polyols, polyurethane polyols and combinations thereof.

Clause 12. The alternative polyurethane composition according to one ofClauses 10 and 11, wherein the catalyst comprises a Cu^(II) catalyst anda reducing agent.

Clause 13. The alternative polyurethane composition according to one ofClauses 10 to 12, wherein the Cu^(II) catalyst is selected from thegroup consisting of copper(II) chloride, CuCl₂[PMDETA], copper(II)bromide, copper(II) iodide, copper(II) sulfate, and copper(II) acetatemonohydrate.

Clause 14. The alternative polyurethane composition according to one ofClauses 10 to 13, wherein the reducing agent is selected from the groupconsisting of triphenyl phosphine, sodium ascorbate, tin(II)2-ethylhexanoate, and hydroquinone.

Clause 15. One of a coating, an adhesive, a sealant, a film, anelastomer, a casting, a foam, and a composite comprising the alternativepolyurethane composition according to any one of Clauses 9 to 14.

Clause 16. A substrate having applied thereto the one of a coating, anadhesive, a sealant, a film, an elastomer, a casting, a foam, and acomposite according to Clause 15.

Clause 17. A process of producing an alternative polyurethanecomposition, the process comprising reacting an azidated polyol and apoly(alkynyl carbamate) allophanate prepolymer, optionally in thepresence of a catalyst, wherein the poly(alkynyl carbamate) allophanateprepolymer comprises a reaction product of poly(alkynyl carbamate)prepolymer and a first alkynol in the presence of a metallo-organiccompound of the formula: M(acac)_(n), wherein M=a metal, acac=anacetylacetonate residue, and n=2 or 3, wherein the poly(alkynylcarbamate) prepolymer comprises a reaction product of a polyisocyanateand a stoichiometric equivalent of a second alkynol, and wherein thepolyisocyanate comprises isocyanate groups and uretdione groups.

Clause 18. The process according to Clause 17, wherein the first alkynoland the second alkynol each independently contain from 3 to 10 carbonatoms.

Clause 19. The process according to one of Clauses 17 and 18, whereinthe first alkynol and the second alkynol are identical or different.

Clause 20. The process according to any one of Clauses 17 to 19, whereinthe first alkynol and the second alkynol are selected from the groupconsisting propargyl alcohol, 2-hydroxyethylpropiolate, and isomers ofany of these; or mixtures of any of these.

Clause 21. The process according to any one of Clauses 17 to 20, whereinM is selected from the group consisting of aluminum, calcium, chromium,cobalt, copper, iron, magnesium, manganese, nickel, titanium, vanadium,zinc, and zirconium.

Clause 22. The process according to any one of Clauses 17 to 21, whereinthe metallo-organic compound comprises zinc acetylacetonate.

Clause 23. The process according to any one of Clauses 17 to 22, whereinthe polyisocyanate is selected from the group consisting of1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate,2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylenediisocyanate, cyclohexane-1,3-diisocyanate,cyclohexane-1,4-diisocyanate, 1-isocyanato-2-isocyanato-methylcyclopentane, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate or IPDI),bis-(4-isocyanatocyclohexyl)methane,1,3-bis(isocyanatomethyl)-cyclohexane,1,4-bis(isocyanatomethyl)-cyclohexane,bis-(4-isocyanato-3-methyl-cyclohexyl)-methane,α,α,α′,α′-tetramethyl-1,3-xylene diisocyanate,α,α,α′,α′-tetramethy-1,4-xylene diisocyanate,1-isocyanato-1-methyl-4(3)-isocyanato-methyl cyclohexane,2,4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate,toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), pentanediisocyanate (PDI)—bio-based), and, isomers of any of these; or mixturesof any of these.

Clause 24. The process according to any one of Clauses 17 to 23, whereinthe uretdione groups are selected from the group consisting of aliphatic1,6-hexamethylene diisocyanate (HDI) uretdiones, aromatic toluenediisocyanate (TDI) uretdiones, and aliphatic isophorone diisocyanate(IPDI) uretdiones.

Clause 25. The process according to any one of Clauses 17 to 24, whereinthe azidated polyol is a reaction product of a polyol and an azide.

Clause 26. The process according to Clause 25, wherein the polyol isselected from the group consisting of polyalkylene ether polyols,polyester polyols, hydroxyl containing polycaprolactones,hydroxyl-containing (meth)acrylic polymers, polycarbonate polyols,polyurethane polyols and combinations thereof.

Clause 27. The process according to any one of Clauses 17 to 26, whereinthe catalyst comprises a Cu^(II) catalyst and a reducing agent.

Clause 28. The process according to Clause 27, wherein the Cu^(II)catalyst is selected from the group consisting of copper(II) chloride,CuCl₂[PMDETA], copper(II) bromide, copper(II) iodide, copper(II)sulfate, and copper(II) acetate monohydrate.

Clause 29. The process according to one of Clauses 27 and 28, whereinthe reducing agent is selected from the group consisting of triphenylphosphine, sodium ascorbate, tin(II) 2-ethylhexanoate, and hydroquinone.

Clause 30. One of a coating, an adhesive, a sealant, a film, anelastomer, a casting, a foam, and a composite comprising the alternativepolyurethane composition made according to the process of any one ofClauses 17 to 29.

Clause 31. A substrate having applied thereto the one of a coating, anadhesive, a sealant, a film, an elastomer, a casting, a foam, and acomposite according to Clause 30.

What is claimed is:
 1. A poly(alkynyl carbamate) allophanate prepolymercomprising a reaction product of a first alkynol and a poly(alkynylcarbamate) prepolymer, in the presence of a metallo-organic compound ofthe formula:M(acac)_(n), wherein, M=a metal, acac=an acetylacetonate residue, n=2 or3, wherein the poly(alkynyl carbamate) prepolymer comprises a reactionproduct of a polyisocyanate and a stoichiometric equivalent of a secondalkynol, and wherein the polyisocyanate comprises isocyanate groups anduretdione groups.
 2. The poly(alkynyl carbamate) allophanate prepolymeraccording to claim 1, wherein the first alkynol and the second alkynoleach independently contain from 3 to 10 carbon atoms.
 3. Thepoly(alkynyl carbamate) allophanate prepolymer according to claim 1,wherein the first alkynol and the second alkynol are identical ordifferent.
 4. The poly(alkynyl carbamate) allophanate prepolymeraccording to claim 1, wherein the first alkynol and the second alkynolare selected from the group consisting of propargyl alcohol,2-hydroxyethylpropiolate, and isomers of any of these; or mixtures ofany of these.
 5. The poly(alkynyl carbamate) allophanate prepolymeraccording to claim 1, wherein M is selected from the group consisting ofaluminum, calcium, chromium, cobalt, copper, iron, magnesium, manganese,nickel, titanium, vanadium, zinc, and zirconium.
 6. The poly(alkynylcarbamate) allophanate prepolymer according to claim 1, wherein themetallo-organic compound comprises zinc acetylacetonate.
 7. Thepoly(alkynyl carbamate) allophanate prepolymer according to claim 1,wherein the polyisocyanate is selected from the group consisting of1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate,2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 1,12-dodecamethylenediisocyanate, cyclohexane-1,3-diisocyanate,cyclohexane-1,4-diisocyanate, 1-isocyanato-2-isocyanato-methylcyclopentane, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate or IPDI),bis-(4-isocyanatocyclohexyl)methane,1,3-bis(isocyanatomethyl)-cyclohexane,1,4-bis(isocyanatomethyl)-cyclohexane,bis-(4-isocyanato-3-methyl-cyclohexyl)-methane,α,α,α′,α′-tetramethyl-1,3-xylene diisocyanate,α,α,α′,α′-tetramethy-1,4-xylene diisocyanate,1-isocyanato-1-methyl-4(3)-isocyanato-methyl cyclohexane,2,4-hexahydrotoluene diisocyanate, 2,6-hexahydrotoluene diisocyanate,toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), pentanediisocyanate (PDI)—bio-based), and, isomers of any of these; or mixturesof any of these.
 8. The poly(alkynyl carbamate) allophanate prepolymeraccording to claim 1, wherein the uretdione groups are selected from thegroup consisting of aliphatic 1,6-hexamethylene diisocyanate (HDI)uretdiones, aromatic toluene diisocyanate (TDI) uretdiones, andaliphatic isophorone diisocyanate (IPDI) uretdiones.
 9. An alternativepolyurethane composition comprising a reaction product of an azidatedpolyol and the poly(alkynyl carbamate) allophanate prepolymer accordingto claim 1, optionally in the presence of a catalyst.
 10. Thealternative polyurethane composition according to claim 9, wherein theazidated polyol is a reaction product of a polyol and an azide.
 11. Thealternative polyurethane composition according to claim 10, wherein thepolyol is selected from the group consisting of polyalkylene etherpolyols, polyester polyols, hydroxyl containing polycaprolactones,hydroxyl-containing (meth)acrylic polymers, polycarbonate polyols,polyurethane polyols and combinations thereof.
 12. The alternativepolyurethane composition according claim 10, wherein the catalystcomprises a Cu^(II) catalyst and a reducing agent.
 13. The alternativepolyurethane composition according to claim 10, wherein the Cu^(II)catalyst is selected from the group consisting of copper(II) chloride,CuCl₂[PMDETA], copper(II) bromide, copper(II) iodide, copper(II)sulfate, and copper(II) acetate monohydrate.
 14. The alternativepolyurethane composition according to claim 10, wherein the reducingagent is selected from the group consisting of triphenyl phosphine,sodium ascorbate, tin(II) 2-ethylhexanoate, and hydroquinone.
 15. One ofa coating, an adhesive, a sealant, a film, an elastomer, a casting, afoam, and a composite comprising the alternative polyurethanecomposition according to claim
 9. 16. A substrate having applied theretothe one of a coating, an adhesive, a sealant, a film, an elastomer, acasting, a foam, and a composite according to claim
 15. 17. A process ofproducing an alternative polyurethane composition, the processcomprising reacting: an azidated polyol; and a poly(alkynyl carbamate)allophanate prepolymer, optionally, in the presence of a catalyst,wherein the poly(alkynyl carbamate) allophanate prepolymer comprises areaction product of poly(alkynyl carbamate) prepolymer and a firstalkynol in the presence of a metallo-organic compound of the formula:M(acac)_(n), wherein, M=a metal, acac=an acetylacetonate residue, andn=2 or 3, wherein the poly(alkynyl carbamate) prepolymer comprises areaction product of a polyisocyanate and a stoichiometric equivalent ofa second alkynol, and wherein the polyisocyanate comprises isocyanategroups and uretdione groups.
 18. The process according to claim 17,wherein the first alkynol and the second alkynol each independentlycontain from 3 to 10 carbon atoms.
 19. The process according to claim17, wherein the first alkynol and the second alkynol are identical ordifferent.
 20. The process according to claim 17, wherein the firstalkynol and the second alkynol are selected from the group consistingpropargyl alcohol, 2-hydroxyethylpropiolate, and isomers of any ofthese; or mixtures of any of these.
 21. The process according to claim17, wherein M is selected from the group consisting of aluminum,calcium, chromium, cobalt, copper, iron, magnesium, manganese, nickel,titanium, vanadium, zinc, and zirconium.
 22. The process according toclaim 17, wherein the metallo-organic compound comprises zincacetylacetonate.
 23. One of a coating, an adhesive, a sealant, a film,an elastomer, a casting, a foam, and a composite comprising thealternative polyurethane composition made according to the process ofclaim
 17. 24. A substrate having applied thereto the one of a coating,an adhesive, a sealant, a film, an elastomer, a casting, a foam, and acomposite according to claim 23.